Azo compounds having a 2-nitro-4-phenylsulfamoyldiphenyl amine nucleus

ABSTRACT

Compounds of the formula   WHEREIN E is phenyl, substituted phenyl, naphthyl, methylsulfonylnaphthyl, thiazolyl, substituted thiazolyl, benzothiazolyl, substituted benzothiazolyl, pyrazolyl, substituted pyrazolyl, 4-carbamoylimidazolyl, 4-phenyl-1,3,5thiadiazolyl, thienyl, quinolyl or tetrazolyl, F is phenyl, naphthyl, thiazolyl, benzothiazolyl, pyrazolyl, imidazolyl, thiadiazolyl, thienyl, quinolyl, tetrazolyl,or 1anilino-1,3-dioxobutyryl-2, or a substituted derivative thereof, X is hydrogen, alkyl or substituted alkyl, M IS 0 OR 1, AND N IS 0 OR 1, WITH THE PROVISO THAT M + N IS 1 OR 2, AND WHEREIN Rings A, B and D may bear additional substituents. These compounds are outstandingly suitable for dyeing and printing fibres consisting of synthetic or semi-synthetic, hydrophobic organic compounds of high molecular weight, and of textile materials manufactured with these fibres.

nited States Patent Altermatt [451 Feb. 11, 1975 AZO COMPOUNDS HAVING A 2-NITRO-4-PHENYLSULFAMOYLDIPI-IE- NYL AMINE NUCLEUS Ruedi Altermatt, Hauptstrasse 65, Tecknau, Basel-Land, Switzerland Filed: Dec. 2, 1971 Appl. No.: 204,382

Related US. Application Data Continuation of Ser. No. 851,444, Aug. 19, 1969, abandoned.

Inventor:

Foreign Application Priority Data Aug. 30, 1968 Switzerland 13051/68 Dec. 19, 1968 Switzerland 18944l/68 Dec. 19, 1968 Switzerland 18943/68 US. Cl 260/205, 260/152, 260/156, 260/155, 260/157, 260/158, 260/160, 260/162, 260/163, 260/174, 260/176, 260/193, 260/196, 260/206, 260/207,

260/207.1, 260/556 N, 8/26, 8/41 B, 8/41 C, 8/50 Int. Cl. C09b 43/00, C09b 43/12 Field of Search 260/205, 206, 207, 207.1, 260/207.5, 207.3, 196

References Cited UNITED STATES PATENTS 3/1959 Merian 260/205 X 6/1970 Dimroth et a1. 260/206 10/1970 Altermatt et al. 260/207.1 5/1972 Liechti 260/207 X FOR EIGN PATENTS OR APPLICATIONS 4/1960 Switzerland 260/205 Primary ExaminerLorraine A. Weinberger Assistant Examiner-C. F. Warren Attorney, Agent, or Firm--Gerald D. Sharkin; Richard E. Vila; Melvyn M. Kassenoff [57] ABSTRACT Compounds of the formula wherein E is phenyl, substituted phenyl, naphthyl, methylsulfonylnaphthyl, thiazolyl, substituted thiazolyl, benzothiazolyl, substituted with the proviso that m n is 1 or 2, and wherein Rings A, B and D may bear additional substituents. These compounds are outstandingly suitable for dyeing and printing fibres consisting of synthetic or semisynthetic, hydrophobic organic compounds of high molecular weight, and of textile materials manufactured with these fibres.

15 Claims, No Drawings AZO COMPOUNDS HAVING A HENY LEAMQY DIPH YL AMINE NUCLEUS where,

E stands for a phenyl radical which may be substituted by chlorine or bromine atoms, lower alkyl, lower alkoxy, trifluoromethyl, nitro, cyano, thiocyano, phenoxy, formyl, acetyl, benzoyl, lower alkylsulphonyl, lower hydroxyalkylsulphonyl, benzylsulphonyl, aminosulphonyl, methylaminosulphonyl, cyanoethylaminosulphonyl, hydroxyethylaminosulphonyl, phenylaminosulphonyl, formylamino, lower alkanoylamino, chloropropionylamino, lower alkylsulphonylamino, lower alkoxycarbonyl, benzyloxycarbonyl, lower alkoxycarbonylamino, aminocarbonyl, lower a1- kylaminocarbonyl or phenylaminocarbonyl groups; a naphthalene radical which may be substituted by a methylsulphonyl group; a thiazole radical which may be substituted by chlorine or bromine atoms, methyl, methoxy, nitro, methylsulphonyl or trifluoromethyl groups; a benzothiazole radical which may be substituted by chlorine or bromine atoms, or a nitro, cyano, methylsulphonyl, methoxy, trifluoromethyl, aminosulphonyl, lower alkylaminosulphonyl; hydroxyethylaminosulphonyl or a methoxypropylaminosulphonyl group; a pyrazole radical which may be substituted by methyl, benzyl or phenyl groups; a 4-aminocarbonylimidazole radical, a 4-phenylthiadiazole-(1,3,5)-radical, a thiophene radical, a quinoline radical or a tetrazole radical;

F for a phenyl, naphthyl, thiazolyl, benzothiazolyl,

pyrazolyl, imidazolyl, thiadiazolyl, thienyl, quinolyl, tetrazolyl or acetoacetic acid anilide radical which may be substituted;

X for a hydrogen atom or an optionally substituted alkyl group;

m for 0 or 1 and n for O or 1,

where the sum of m and n is at least 1; and where the rings A, B and D may bear further substituents and the molecule is free from sulphonic acid groups.

In preferable dyestuffs of formula (I), the symbols have the following meanings:

E stands for a phenyl radical which may be substituted by chlorine or bromine atoms, lower alkyl, lower alkoxy, trifluoromethyl, nitro, cyano, thiocyano, phenoxy, formyl, acetyl, benzoyl, lower alkylsulphonyl, lower hydroxyalkylsulphonyl, benzylsulphonyl, cyanoethylaminosulfonyl (cyanoethylsulfamoyl), N-hydroxyethy1aminosulfonyl (N-hydroxyethylsulfamoyl), phenylaminosulfonyl (phenylsulfamoyl), formylamino (formamido) lower alkanoylamino, chloropropionylamino (chloropropionamido), lower alkylsulphonylamino, lower alkoxycarbonyl, benzyloxycarbonyl, lower alkoxycarbonylamino, aminocarbonyl (carbamoyl), lower alkylaminocarbonyl (alkylcarbamoyl) or phenylaminocarbonyl (phenylcarbamoyl) groups; a naphthalene radical which may be substituted by a methylsulphonyl group; a thiazole radical which may be substituted by chlorine or bromine atoms, methyl, methoxy, nitro, methylsulphonyl or trifluoromethyl groups; a benzothiazole radical which may be substituted by chlorine or bromine atoms, nitro, cyano, methylsulphonyl, methoxy, trifluoromethyl, aminosulphonyl, lower alkylaminosulphonyl, hydroxyethylaminosulphonyl or a methoxypropylaminosul'phonyl group; a pyrazole radical which may be substituted by methyl, benzyl or phenyl groups; a 4- aminocarbonylimidazole radical; a 4- phenylthiadiazole-( 1,3,5) radical; a thiophene radical, a quinoline radical or a tetrazole radical;

F for a phenyl radical which may be substituted by chlorine or bromine atoms, lower alkyl, lower alkoxy, phenoxy, trifluoromethyl, thiocyano, cyano, nitro, hydroxyl, formyl, acetyl, benzoyl, lower a1- kylsulphonyl, hydroxyethylsulphonyl, benzylsulphonyl, aminosulphonyl, lower alkylaminosulphonyl, cyanoethyl sulfamoyl, hydroxyethylaminosulphonyl, phenylaminosulphonyl, lower alkylamino, cyanethylamino, formylamino, lower a1- kanoylamino, chloropropionylamino, methylsulphonylamino, lower alkoxycarbonyl, benzyloxycarbonyl, lower alkoxycarbonylamino, aminocarbonyl, lower alkylaminocarbonyl or phenylaminocarbonyl groups; a naphthalene radical which may be substituted by a methylsulphonyl group; a benzothiazole radical which may be substituted by chlorine or bromine atoms or a nitro, cyano, methylsulphonyl, methoxy, trifluoromethyl, aminosulphonyl, methylaminosulphonyl, ethylaminosulphonyl, hydroxyethylaminosulphonyl or methoxypropylaminosulphonyl group; a pyrazole radical which may be substituted by lower alkyl, hydroxyl, amino, carboxylic acid amide or phenyl groups: a 4-aminocarbonylimidazole radical: a 4-phenylthiadiazole-(1,3,5) radical; a thiophene radical; a quinoline radical; a hydroxyquinoline radical; a tetrazole radical or an acetoacetic acid anilide radical;

X for a hydrogen atom or a lower alkyl group which may be substituted by chlorine or bromine atoms, hydroxyl, cyano, lower alkanoyloxy, benzoyloxy, lower alkoxycarbonyloxy, lower alkoxycarbonyl, aminocarbonyl, benzyloxycarbonyloxy, lower alkoxy, phenoxy, pyridyl, methylaminocarbonyloxy (methylcarbamoyloxy) or phenylaminocarbonyloxy (phenylcarbamoyloxy) groups;

m for 0 or 1 and n for 0 or 1,

where the sum of m and n is at least 1; the ring A may bear as substituents chlorine or bromine atoms, lower alkyl, lower alkoxy, formylamino, lower alkanoylamino, benzoylamino, lower alkoxycarbonylamino, benzyloxycarbonylamino or chloropropionylamino groups; the ring B may bear a further nitro group; the ring D may bear chlorine or bromine atoms, lower alkyl, lower alkoxy, phenoxy, hydroxyl, cyano, nitro, thiocyano, hydroxyethoxy, lower alkanoyloxyethoxy, formylamino, lower alkanoylamino, benzoylamino, lower alkylsulphonyl, benzylsulphonyl, phe- The term lower indicates that the respective groups contain 1, 2, 3 or 4 carbon atoms.

The azo compounds of the formula (l) are produced by condensation of one mole of a compound of formula OQN (I where Hal represents a chlorine or bromine atom, with one mole of an amine of formula (F-N=N)n 1'5 25 D N1I (III) and one mole ofan amine of the formula (EN=N)m 5 A NII2 The condensation reaction is generally conducted in an inert solvent, e.g. water, ethanol, n-butanol, benzyl alcohol, ethylene glycol, polyethylene glycol, benzene, toluene, xylene, chlorobenzene etc., at temperatures in the range of 25C to 200C. It is usually of advantage to include an acid-binding agent in the reaction mixture, e.g. alkali, carbonates, bicarbonates or acetates, magnesium oxide or calcium oxide.

Since the halogen atom attached to the S0 group in the compound of formula (II) is more highly reactive than the halogen atom bound to the nucleus, the first noted amine of formula (III) is bound to the SO group while the amine of formula (IV) is subsequently bound directly to the nucleus B. It is desirable to effect the first stage of the reaction at a temperature below 100C and the second stage in the range of about 80C to 200C, employing an autoclave if necessary.

A second mode of operation for producing compounds of formula (I) is to melt one mole of a compound of the formula and one mole of an amine of formula (IV) and to condense the two in the presence of one of the aforenamed acid-binding agents at a suitable temperature between 100C and 220C A further synthetic route to compounds of formula (I) consists in condensing one mole of a compound of the formula and one mole of an amine of formula (IV), converting the resulting compound with a halogenating agent, e.g. phosphorus trichloride or thionyl chloride, into the sulphonic acid chloride of formula NO: (VII) and condensing this with one mole of an amine of formula (III). Here the condensation reaction of the compound of formula (VI) with the amine of formula (IV) is carried out, preferably in one of the aforenamed solvents, at temperatures in the range of about 30C to 200C, whilst the condensation of the compound of formula (VII) with the amine of formula (III) is effected preferably in the same medium in the range of 25C to C.

A further method of production yielding compounds of formula (I) in which n=l consists in the diazotization of a compound of formula (VIII) followed by coupling with a compound of the formula In the especially preferred dyes of formula (I) the sum .with 1 mole of a mixture of different compounds of formula or by reacting 1 mole of a mixture of different compounds of the formula with 1 mole of a compound of the formula It is of great advantage to convert the new dyes into dye preparations before their application, using known methods for this purpose, e.g. grinding in the presence of dispersing agents and/or fillers, with subsequent vacuum or spray drying if dry preparations are desired. After the addition of a suitable volume of water the dyes can be applied to the substrate by exhaustion dyeing, pad dyeing or printing methods at long or short liquor ratio.

From aqueous dispersions the dyes build up excellently on textile materials consisting of synthetic or semi-synthetic organic substances, of hydrophobic character and high molecular weight. They are especially suitable for dyeing and printing textiles of linear aromatic polyester fibres, cellulose diacetate, cellulose triacetate and polyamide fibres. They are also dyeable on polyolefins.

The known exhaustion dyeing, pad dyeing and printing methods are employed, for example the process described in French Pat. No. 1,445,371.

The dyeings obtained are of yellow shade and are extremely fast, showing excellent fastness to heat treatments (thermofixation, sublimation, pleating), gas fumes, cross dyeing, dry cleaning, chlorine and wet tests such as washing, water and perspiration. They are highly stable to the conditions of the pre-cure and postcure permanent press finishing process. The dischargeability and the reserve of wool and cotton are good. Their fastness to light is outstandingly good, even in pale shades, which makes the new dyes well suitable as components for the production of fashionable pastel combination shades. At temperatures in the range of 80C to 140C the dyes are resistant to reduction by boiling: this stability is not adversely affected by the liquor ratio or by the presence of dyeing accelerants.

1n the following Examples the parts are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 A mixture of 25.6 parts of l-chloro-2-nitrobenzene- 4-sulphonic acid chloride. 19.7 parts of 4-amino-l,1'- azobenzene, 250 parts of ethylene glycol and 20 parts of anhydrous sodium acetate is raised to 50 in 30 minutes and stirred at this temperature for 2 hours. 12.8 parts of l-amino-4-chlorobenzene are added to the reaction mixture and the temperature is then increased over 1 hour to 150. After stirring for 3 hours at 150-155 the reaction mixture is allowed to cool to room temperature, on which the dye settles out in crystalline form. It is filtered off, washed with a little ethano! and then with hot water, and finally dried. On synthetic fibers the dye thus obtained gives dyeings of yellow shade which have excel1ent,fastness properties EXAMPLE 2.

A mixture of 31.3 parts of l-chloro-2-nitrobenzene- 4-sulphonic acid phenylamide. 19.7 parts of 4-amino 1,1'-azobenzene, parts of polyethylene glycol and 10 parts of anhydrous sodium acetate is raised to 160 in 30 minutes with vigorous stirring, stirred for a further 24 hours at l60-165 and then allowed to cool to about 70. At this temperature the reaction mixture is diluted with 100 parts of ethanol, after which 40 parts of water are added very slowly. The dye settles out and after 2 hours it is filtered off, washed with some ethanol and then with hot water, and dried. The pure dye, applied to synthetic fibres,.gives reddish yellow dyeings having excellent fastness properties.

EXAMPLE 3 A mixture of 31.7 parts of the compound of the formula the production of which is described in Example 1, 9.3 parts of aniline. 200 parts of ethylene glycol and 10 parts of anhydrous sodium acetate is raised over 40 minutes to 145 and reacted for 2 hours at 145150 with stirring. After this time the mixture is allowed to cool to 2030. The dye settling out in crystalline form and is filtered off, washed with some ethanol and then with hot water and subsequently dried. Yellow dyeings of excellent all-round fastness are obtained with thin dye on synthetic fibre materials.

EXAMPLE 4 A mixture of 25.6 parts of l-ch.loro-2-nitrobenzene- 4-sulphonic acid chloride. 29.4 parts of 4-amino-l,1 azobenzene, 250 parts of ethylene glycol and 20 parts of anhydrous sodium acetate is raised to in 2 hours with thorough stirring. The temperature is held at 80 for 1 hour, then at 150 for 3 hours and subsequently at 170 for 2 hours. After this time the reaction mixture is allowed to cool to 70 and is diluted with parts of ethanol. Cooling is allowed to continue and the pre- 1 cipitated dye is filtered off at room temperature. It is washed with ethanol and then with hot water and dried. The dye thus obtained dyes synthetic fibres in yellow shades with excellent fastness properties.

EXAMPLE 5 A mixture of 32.7 parts of l-chloro-Z-nitrobenzene- 4-sulphonic acid-(3-methyl)-phenylamide, 34.3 parts of 1-chloro-2-nitrobenzene-4-sulphonic acid-(2'- methoxy)-phenylamide. 39.4 parts of 4-amino-l ,1 azobenzene and 30 parts of anhydrous sodium acetate is brought to l70l80 over 30 minutes, on which a melt is formed which is stirred for 8-12 hours at the same temperature. It is then allowed to cool to at which point 40 parts of ethylene glycol are added, and then to 90, when 80 parts of ethanol are added, followed after a few minutes by 40 parts of water. The mixture is vigorously stirred for 1 hour at 80, after which time the precipitated product is filtered off. The filtercake is washed with a little cold ethanol and then with ample hot water and finally dried. The dye mixture thus obtained gives dyeings of reddish yellow shade on polyester fibres which have excellent fastness properties. 7

EXAMPLE 6 A mixture of 31.3 parts of 1-chloro-2-nitrobenzene- 4-sulphonic acid phenylamide, 34.3 parts of l-chloro- 2-nitrobenzene-4-sulphonic acid-(2-methoxy)- phenylamide. 32.7 parts of 1-chloro-2-nitrobenzene-4- sulphonic acid-(3'-methyl)-phenylamide, 59.1 parts 4-amino-l,1'-azobenzene and 45 parts of anhydrous sodium acetate is raised to 160-180 in 30 minutes to form a melt which is stirred for 8 to 12 hours at this temperature. it is then allowed to cool to 150, on which 70 parts of ethylene glycol are added, and then further to 90, at which point 150 parts of ethanol are added, followed after a few minutes by 70 parts of water. Vigorous stirring is maintained for 1 hour at 80 causing precipitation of the dye of mixed constitution formed by the reaction. The filtercake is washed with cold methanol and then with abundant hot water and finally dried. The dye mixture yielded by this procedure gives dyeings of reddish yellow shade on polyester fibres which have excellent all round fastness.

EXAMPLE 7 A mixture of 37.1 parts of the compound of formula 15 parts of anhydrous sodium acetate and 19.7 parts of 4-amino-l,1-azobenzene is raised to 170 in 30 minutes and the resulting melt is stirred for 15 hours at 160-175. After partial cooling to 150 parts of ethylene glycol are added, then cooling is continued to 90 for the addition of 50 parts ethanol and after a few minutes 30 parts of water. The mixture is stirred thoroughly for a further hour at 80 which caused the dye to settle out. It is filtered off, washed with a little cold ethanol and then with ample hot water and finally dried. The dye thus obtained dyes synthetic fibres in reddish yellow shades which have excellent fastness properties.

EXAMPLE 8 A mixture of 32.7 parts of l-chloro 2-nitrobenzene-4 -sulphonic acid-(3-methyl)-phenylamide. 35.5 parts of l-chloro-2-nitrobenzene-4-sulphonic acid-N-ethyLN- (3'-methyl)-phenylamide, 39.4 parts of 4-amino-l,1'-

azobenzene and 30 parts of anhydrous sodium acetate is heated up to l70-180 over 30 minutes to form a melt which is stirred for 8-12 hours at the same temperature. It is allowed to cool to 150, on which 40 parts of ethylene glycol are added, then cooling is continued to 90, at which point 80 parts of ethanol and after a few minutes 40 parts of water are added. The mixture is vigorously stirred for 1 hour at 80 and the precipitated product is filtered off, washed with some cold ethanol and then with ample hot water and finally dried. This procedure results in a dye mixture which gives dyeings of reddish yellow shade on polyester fibres having excellent fastness properties.

EXAMPLE 9 A mixture of 39.9 parts of l-bromo-2-nitrobenzene- 4-sulphonic acid-N-ethyI-N-(3-methyl)-phenylamide. 19.7 parts of 4-amino-1,1'-azobenzene and 15 parts of anhydrous sodium acetate is raised to 150 in 30 minutes and the resulting melt stirred for 10 hours at 145-150. It is allowed to cool to 120, on which 20 parts of ethylene glycol are added, and then to 90 for the addition of 40 parts of ethanol followed in a few minutes by 15 parts of water. The mixture is vigorously stirred for 2 hours at -80. The precipitated product is then filtered off, washed with some cold ethanol and then with ample hot water and dried. The dye thus obtained dye synthetic fibres in reddish yellow shades with excellent fastness properties.

EXAMPLE 10 A mixture of 32.7 parts of l-chloro 2-nitrobenzene- 4-sulphonic acid-N-methylphenylamide. 19.7 parts of 4-amino- 1,1 '-azobenzene, parts of polyethylene glycol and 15 parts of anhydrous sodium acetate is raised to 160 in 30 minutes with vigorous stirring and stirred for 24 hours at 160-170. lt is then allowed to cool to about 70. At this temperature the reaction mixture is diluted with parts of ethanol and when 2 hours have elapsed the precipitated dye is filtered off. It is washed with a little ethanol and then with hot water and dried. The purified dye gives dyeings of reddish yellow shade on synthetic fibres showing excellent allround fastness.

EXAMPLE 1 l A mixture of 40 parts of l-chloro-2,6- dinitrobenZene-4-sulphonic acid-N-ethyl-N-( 3 methyl)-phenylamide, 19.7 parts of 4-amino-l,1'- azobenzene. 15 parts of anhydrous sodium acetate and 200 parts of ethylene glycol is brought to stirred for 2-3 hours at 140150 and then allowed to cool to 2030. The dye, which settles out in crystalline form, is filtered off, washed with some ethanol and then with hot water and dried. On synthetic fibres the dye obtained by this procedu're gives dyeings of yellow shade having outstandingly good fastness properties.

DYEING EXAMPLE 1 A mixture of 7 parts of the dye obtained as specified in Example 1, 4 parts of sodium dinaphthylmethanedisulphonate, 4 parts of sodium cetylsulphate and 5 parts of sodium sulphate is ground in a ball mill for 48 hours to give a fine powder. Two parts of the powder are dispersed in 3000 parts of water set with 3 parts of a 30 percent solution of a highly sulphonated castor oil and 20 parts of an emulsion of a chlorinated benzene. Into this dyebath 100 parts of a fabric of polyester fibre are entered at 2025, on which the bath temperature is increased to 95100 in about 30 minutes and the fabric dyed for 1 hour at this temperature. It is then removed, washed off, soaped for 15 minutes at 70 with a 0.1 percent solution of an alkylphenylpolyglycol ether, rinsed and dried. A yellow dyeing having excellent fastness properties is obtained.

DYEING EXAMPLE 2 A mixture of 30 parts of the dye obtained as given in Example 2, 40 parts of sodium dinaphthylmethanedisulphonate, 50 parts of sodium cetylsulphate and 50 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours to form a fine powder. 4 Parts of this dye powder are dispersed in 1000 parts of water at 40-50 and 100 parts of a scoured fabric of polyester fibre are entered into the bath. The bath is raised slowly to 130 and the fabric dyed for about 1 hour at this temperature under pressure. Subsequently it is washed off, soaped, rinsed and dried. The yellow dyeing produced on the polyester fabric has excellent fastness properties.

DYEING EXAMPLE 3 A fine aqueous dispersion of 30 parts of the dye mixture obtained by the procedure of Example 6, 70 parts of sodiumdinaphthylmethanedisulphonate and 3 parts of sodium alginate is made up to 1000 parts with water and thoroughly mixed. This padding liquor is applied to a polyester fabric at 20 and after intermediate drying in air at 60-l00 the pad dyeing is fixed by exposure for 60 seconds in a dry air atmosphere at 230. After fixation the fabric is rinsed, soaped, rinsed again and dried. The level yellow dyeing thus produced has good allround fastness.

DYEING EXAMPLE 4 A mixture of 15 parts of the dye of Example 1, 20 parts of sodium dinaphthylmethanedisulphonate, 25 parts of sodium cetylsulphate and 25 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours to form a fine powder. 5 Parts of this dye preparation are dispersed in 4000 parts of water and into this bath 100 parts of a scoured fabric of cellulose triacetate fibre are entered. The bath temperature is raised slowly to 95l00 and the fabric dyed for one hour at this temperature. On removal it is washed off, soaped for minutes at 70 with a 0.1 percent solution of an alkylphenolpolyglycol ether, rinsed and dried. A red dyeing with good fastness properties is obtained.

DYEING EXAMPLE 5 A mixture of 7 parts of the dye of Example 7, 4 parts of sodium dinaphthylmethanedisulphonate, 4 parts of sodium cetylsulphate and 5 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours. A fine powder is formed, 2 parts of which are dispersed in 3000 parts of water containing 3 parts of a 30 percent solution of a highly sulphonated castor oil. At 20-25 100 parts of a cellulose diacetate fabric are entered, the bath is raised to -82 in about 30 minutes and the fabric dyed for 1 hour at this temperature. It is then removed, washed off, soaped, rinsed and dried. A reddish yellow dyeing having good fastness properties is obtained.

DYEING EXAMPLE 6 In a ball mill, a mixture of 7 parts of the dye of Example 7, 13 parts of powder from spent sulphite cellulose liquor and parts of water is ground to a paste which is dried in an injection dryer. 4 Parts of the paste are dispersed in a little water and the dispersion is run through a sieve into a bath of 4000 parts of water set with 4 parts of N-oleyl-N'-hydroxyethyl-N'-(3'-sulpho- 2'-hydroxypropyl)-ethylenediamine. lOO Parts of a fabric of nylon polyamide fibre are entered into the bath at 20 the bath is raised to 100 in. 30 minutes and the fabric dyed for 1 hour at this temperature, with subsequent rinsing and drying. The reddish yellow dyeing thus produced is level and has good fastness properties.

The dyes listed in the following table conform to the general formula Q m m HHU Hm Hm MHZHOO 2 m m m0 mm mm m ZH um -2 z 4 m m m m m r5 m z z j on m m m m m S Z Z m O mO .aomoh 5363M m H mm m m an M 6 z z m m m .326? m m m H m n an m m m m m0 o 69 m m Hm "WU O HHO n: 6Q m m m m 625 mm 05mm d5 $250k n fl w m m m m m m v .32.? m Hm Hm Hm m u 6Q m m Hm mm ZHZ mm 0: 6g HHOII m m Hm m ZH L M an: sfiwu m Hm 5 2 I m I H IW M 95 3.20% Go @925 um 3H JH M M Sm i m 9 "m o m m m m 5 m 5 0 m m m .OQ n m m mm 0!. m m m mww m 00 m m w m 5 0 m m o9 0| m m m m $25 3 35m 3 .32.? nmeuum HH ":0 0 HM i m |ZHZ|OH .Z .OnH m m m m m I IN m O|HHZ O O m mY Z Z .326? m "m0 0 O i m m M i m z z wfi 1 5 afl vm m m m OI: m m Z m 23? m m m m m O 6Q m m H m m Z Z O Q m zm mo 6Q m m m m m 6Q m m m m m 2?" fia m m m m m m EETOQ Z Bo w m W m m m 3 w /I z z q do an m m m m m m 62% a z z 6Q m 2 m m m 525a wd 25m an m m w mo oomz H L fiHU Z Z O a 6Q m HMO Hm m m a 0.5m 333cm no mwmsm .OAH Hm Z Hm Hm m 2 v .OQ m Hm Hm Hm Hm I I I my Z w i n m Z Z m m m m Z 6Q Hm an "MO m m 2' Z am 9 m @HOJHOOONZ i I H H IQ E m0 Q m m o o w I v omomz Q 56 H m E m Q mm mm m m ow mm D m H "MO EOO Hm w 4m Q m ED MO m m Q m EO QOO m m m 3. m- MO m r0 N H on Q mU O m m v i u cm 6Q m i i0 2 50 96 8 25m Q mo Hm mo m Hm zuz bonm -ww Z Z Z Q H m ED HH 1 N? Z 4 Q mm mm mo Hm N Z Q -m-0 mo I m m on n Q Q i QOOOO HMO EOO m m m oc Q m HO MO EOO m m m cv Q O m m m m u 1 3 Q i I -O m m w the uouwoflon to 35cm m JH 3m 3 QEQM The dyes set forth in the following Table ll conform to the formula 5 R2 N02 Ra TABLE ll Example X R, R R, R R R Shade on Polyesterfibre 63 -CH, H,C,-N=N- H H -CH H H reddish yellow 64 do. do. H H H -CH;, H do. 65 do. do. H H H H CH: do. 66 do. do. H H H -CH, do. do. 67 do. do. H H -CH, H do. do. 68 do. do. H H H -C] do. do. 69 do. do. H H Cl H do. do. 70 do. do. H 'H -CH H H do. 71 do. do. H H H -OCH, H do. 72 do. do. H H H H -0CH; do. 73 do. do. H H -OCH;, H do. do. 74 do. do. H H H -OCH do. do. 75 do. do. H H -Cl H H do. 76 do. do. H H H -Cl H do. 77 do. do. H H H H -Cl do. 78 do. do. H H Br H H do. 79 do. do. H H H -'Br H do. 80 do. do. H H H H -Br do. 8| -'CH,CH, do. H H H H H do. 82 do. do. H H CH;, H H do. 83 -CH,CH,CH do. H H do. H H do.

no 23cm 6G I i m E i 35mm mm oEaw v 5 i m 8...: 50 a zH L 2 050 Q m m w D E 0c 2 "m0 2 HH m 1on1... E "E0 owwo \m Z Z MO Q Hm m low}... Q m dw- -2 0 :u .7 7 B Z 6Q HM m Zobll. HH m mo w 1111 wm m 2| Q m m 3m 3 28m m i Z w o wo n m E E0 m m 8 5 m m m m m 8 6Q m m -EU m m ow mm m m HA m SMOOOWZ ob w 8 n m m m 500 Eco 8 8 8 n m m m m 6 8 6Q m m m muo m 8.5% mm 25% 252a md 25% ww 8 m m 50 m mo l H L w i w l n I? E 2 $250M H 3 10 m m U m Essa mm aimm ow z z o mzooo mo mo Q m m 925a ma @Emm mm m m m rl 3055 nmruvwm m m Nm m IZUZIFUJM HHHONHHONWHUI vw 32a 3823 Q 3 7 m m um MAMHdAH mo mo mo Z m o mo moom mo 5 Q m m in m Z Z O QQEOEQ 5 m mofio ow m m M05050 5 6 Z Z o uE Q m 265m m m 4 8 mo mo mo Nfl Z Z O O HHOEO Q m m Eo mo m o mo 5 Z Z Z Z EO n $05000o mo mo o m m 50 mofio000E050 52 E05 [ZHZ 26 fim m m Z o m m m GEQEO -5: m Z u 2 z m 26 m flmzoc m 5 m -m= Q m 20 m m m 3 8 E 5 m oz w w m 8 25% 3 2 m Q 5050 m 4 w m m m m Hofio .00.. in m liggamaoadm m m ew QHOSWOSWO-O| Q m m ED w m 95px 2 38m EOEOEOI n: .BOS? GEUUQMH Hh m o z z m HM Hm zuzluonm nmol IN: Q m m m m m Eoooofiofio 5 32?? m E O Z Z m m MOI s: an m m m m m o ooo mo mo $2 5 i m m m flo mo mo in: .5 m m m m woooooamo mu 2: n i m m m moooosmo mo 63 6Q U: m Hm Hm Mm Nm -m 1R: z 50 A v mo mo n m m m m m 2 ll 2: Qflofio n E m m m m z 2 m: 2 lumofimol 5 H m m m m 8 .5 m i m m i N m u E U HH MHQQQAH w Z Z A m OZ QEO mO Omv 7 6Q i i ..owil. E i ov w Z Z w ozi mo mov I' an i m 12%.... E m ou w Z Z w OZMH WHO HHO M l 6Q m m :21... MM Hm w amm m Z Z A w OZX HHOV 6G i m 25 mm 36m m m m Z Z m OZHMQMO 1 6Q .m HA HMO m H fi n m Z Z w OZQH .5 m :Eofioxom m m m w z z q w ofio i .onH HH QWOvy/ OW m HM HH 0U- mg m z z a 0 Z 5 H moo mo mofiomzm d m i E w Z O mO 2| .5 m momz om m m m m z z fi omz 2| 6Q QHOI ED m m m onwwmoamm 95: 35922 SH W Sm m m Sm mm :0 3am SWZ O m Z Z 5Q m :8.-. i i 5 3 db mo mo mo o w O Z Z 0Q m :81... i m E u m: @926 mg H I m m 5 m 2 v: mo mo o wHOJA Z 6Q i av 1%.--. m m E H ou 6Q i .467... H N W O WOOOOEZ 22 3 25m m5 QQ m 4 i m NO MOOOONZ QHO HO EA mu o O O Z Z m m o :8.-- m 5| m 5000 o mo mo 9: Z Z 6 m O 6 M 6 2 m m floooc mo mu 52 mmwolo H I 6Q Hm O 12...... HH 3H0 M "NO O mHOQHU m m 0 w Z Z 6Q E 2 O 253 8 25m m H m 0 O o DMZ 2 Us: 5 m 5050 Q QZ Z 5 0 m m Eo o omz 2 9: mmU mmnw z z m O m o oomz m m m B 2 m w:

ZHZI. Hm O OmmOmZ Hm um m mOmmmO 3H m a G H mm law}--- mm W "m0 m3 5 2 1.. Q M Q 2.67--- H i 6 l m 2 Esq m cron 5m 3m Jm m "M .N N :c 25am B E u 1 HM HQQQH.

muooo z z 5 m m m m m 268 8 m NE SEOEOQOmZ O Z Z 8 m 8 m m m 5080 m o o omz OlA z .5 m 8 m m m m o oo08550 82 m 05 o o OmZ OZ Z .5 3 w m m m mofio808550 2: mQQQETAUiA Z .5 m Ee m m moooo mo mo 9: omomz myz z 5 moo m m m m mu mo 2: omo o z z .5 m 8 m m m m o mz o m O Z Z Q m :81... m m m m xmofiofiovz om o z 529% m on 2. m H m m 1 6 mo mofiomz o w A vz z 58 m m 268 3 85 m m m xzo mofiovz ow o z z .02 HH HHHO| Hm mo HM ov mww zo mo momz o m O Z Z 6Q m m m m m ow 6 6Q HH mo m mo HH ow s 5.8825 wQz z 6Q m m m m H ow m2 m omz o U QZ Z 6Q m m m E HM on m: momz o wQ Z Z 6Q m I HH #0 m ow n 3pm 2823 m mm 3m 3 K Example X R R2 R3 R4 R5 R6 Shade on Poly- I ester fibre 223 CH CH H C -N=N- H H H -SO,N(CH3)1 H reddish yellow 224 do. do. -CH;, H H -SO,N(CH,CH},)2 H do. 225 do. do. do H H COCH3 H do. 226 -CH; do. do. H H -CO-C6H H do. 227 do. do. do. H H -CONH H do. 227a do. do. do H H -CONHCH3 H do. 228 -CH,CH do. H H H CON(CH )z H do. 229 do. do. H H H -CONHCH2CH3 H do. 230 do. do. H H H C0N(CHg H3)z H do. 231 -CH,CH,CH do. H H H -CONHCH,CH, H do.

CHZOCHS R N02 3 X I R1 -NH S O21I R5 The. dyes defmed m the following Table ll] conform to the general formula R; N02 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 having the formula
 3. A compound according to claim 1 wherein E'''' is phenyl or substituted phenyl having 1 or 2 substituents, wherein each substituent of substituted phenyl is independently chloro, bromo, lower alkyl, lower alkoxy, trifluoromethyl, cyano, thiocyano, phenoxy, formyl, acetyl, benzoyl, lower alkylsulfonyl, lower hydroxyalkylsulfonyl, benzylsulfonyl, sulfamoyl, lower alkylsulfamoyl, cyanoethylsulfamoyl, hydroxyethylsulfamoyl, dilower alkylsulfamoyl, N,N-di(cyanoethyl)sulfamoyl, N,N-di(hydroxyethylsulfamoyl, phenylsulfamoyl, formamido, lower alkanoylamino, chloropropionamido, benzamido, lower alkylsulfonylamino, lower alkoxycarbonyl, benzyloxycarbonyl, lower alkoxycarbonylamino, carbamoyl, lower alkylcarbamoyl, dilower alkylcarbamoyl or phenylcarbamoyl, and F'''' is phenyl or substituted phenyl having 1 or 2 substituents, wherein each substituent of substituted phenyl is independently chloro, bromo, lower alkyl, lower alkoxy, phenoxy, trifluoromethyl, thiocyano, cyano, hydroxy, formyl, acetyl, benzoyl, lower alkylsulfonyl, hydroxyethylsulfonyl, benzylsulfonyl, sulfamoyl, lower alkylsulfamoyl, cyanoethylsulfamoyl, hydroxyethylsulfamoyl, dilower alkylsulfamoyl, N,N-di(cyanoethyl)sulfamoyl, N,N-di(hydroxyethyl)sulfamoyl, phenylsulfamoyl, lower alkylamino, cyanoethylamino, dilower alkylamino, N,N-di(cyanoethyl)amino, N-ethyl-N-cyanoethylamino, N,N-di(hydroxyethyl)amino, formamido, lower alkanoylamino, chloropropionamido, benzamido, methylsulfonylamino, lower alkoxycarbonyl, benzyloxycarbonyl, lower alkoxycarbonylamino, carbamoyl, lower alkylcarbamoyl, dilower alkylcarbamoyl or phenylcarbamoyl.
 4. A compound according to Claim 1 having the formula
 5. A compound according to claim 4 having the formula
 6. A compound according to claim 4 having the formula
 7. The compound according to claim 6 having the formula
 8. The compound according to claim 6 having the formula
 9. The compound according to claim 6 having the formula
 10. The compound according to claim 6 having the formula
 11. The compound according to claim 6 having the formula
 12. The compound according to claim 6 having the formula
 13. The compound according to claim 6 having the formula
 14. A compound according to claim 1 having the formula
 15. The compound according to claim 14 having The formula 